Process of treating complex zinc-lead ores



S. GANELIN.

l PROCESS oF TRE/mwa COMPLEX ZINC LEAD 035s.

APPLICATION FILED MAY 6, i919.

Patented Nov. 15, 1921.

A UNITED STATES SOLOMON GANELIN, 0F

BROOKLYN, NEW YORI.

' PROCESSKOF TREATING COMPLEX ZINC-LED CRES.

' Application' tiled May 6,

To all whom it may concer/n Beit known that I, SOLOMON GANELIN, a citizen of the United States, residing at Brooklyn, New York, in the county of Kings, State of New York, have invented certain new and useful' Improvements` in Processes of Treating Complex Zinc-Lead Ores; and I do hereby declare the followin to be a full, clear, and exact description o the invention, such as will enable others skilled in the art to which it appertains to make and use the same.

This invention relates to the recovery of lead and silver and blende from complex ores and Vmetallurgical or metalliferous products'and relates more especially to the treatment o ilead-zinc ores or lead-zinc products often associated in nature with silver or pyrites or both.

This invention relates in the first place to the treatment of sulfid ores and products but can also be easil adapted for treatment of such materials 1n which the lead and silver are in form of oxids or carbonates or in which the lead and silver are combined with antimony or arsenic.

The object of present invention is rot only the recovery of lead and silver from the mentioned materials but also the recovery of a lead free blende the same freed also from the most of the associated pyrites.

The presence of too much pyrites renders difficult and inexpedient the treatment ,of the resulting blende while a lead free blendc is important because such a blende yields lead free products such as lead free spelter or lead free zinc oxid which are increasingly important in the arts and industries particularly in the manufacture of brass for certain purposes such as spinning brass andl cartridge ycases while zinc oxid free "from lead is an essential in the rubber industry.

A further object of `present invention is to separate and remove from the ore alland any antimony or arsenic which are often present in lead-zinc ores and which then contaminate both the lead and the zinc deriving from such ores. The object of this invention is rather to recover the lead as well as the blende in a particularly pure state so that neither lead nor the zinc subsequently to be recovered from the blende shall have to be subjected to the costly metal refining process.

The present invention constitutes a com- Specication of Letters Patent.

Patented Nov. 15,1921. 191s. serial No. 295,155.

posite process consisting of at least three` steps or parts when a lead-zinc material 1sl treated not containing any silver or pyrites,

each of the latter ingredients if present requiring a separate step or part, for its lseparation or lrecovery, so that for the treatment of a lead-zinc material containing also silver and pyrites the present process is accomplished in live separate steps or parts.

First step is a chloridizing operation for 'the sake of converting of all the lead and silver as well as the antimony and arsenic contained in the ore into chlorids and consists in addin to the ore such an amount of zinc chlori or of any of its double salts that the chlorin of the zinc chlorid is equivalent to the sulfids of lead, silver, antimony and arsenic present n the ore, and by heating said admixture under exclusion of air to a temperature of about 400-500 C. mixing or agitating the same in the course of this heating operation `and allowing the volatilating chlorids of antimony and arsenic to .escape and to separate from said admixture. Y

Second step consists in leaching out the chloridized mass of the first step for the purpose of extracting all the lead and silver chlorids (if silver is also present) and is accomplished by using preferably concentrated metal chlorid solutions which aregood solvents for lead and silver chlorids and by taking special measures to prevent the reconversion of the lead and silver chlorids back into their insoluble sulfids (which invariably occurs when no measures are taken) so as to prevent losses in lead and silver as Well as to prevent that the residual blende shall be contaminated with lead.

Third part of theprocess has for its obj ect the recovery of the lead in a pure metallic and marketable form from the leached out lead chlorid by the use of metallic zinc (which may be partly replaced by the electric current) whereby the zinc chlorid used up in the first step is simultaneously recovered.

Fourth part of the process concerns the separation of the silver from its leaching solution if the ore treated contained also an appreciable amount of silver. To this part belongs also the regeneration in said leaching solution of the active chlorin which chlorin is necessary for the complete extraction of the silver from the ore and which `known by myself long being used up at leach operation has to be regenerated each time.

Fifth or iron separation part of the process consists in a magnetic dressing of the blende left after the leaching operation in order to free it of most of its pyrites' if the original ore treated contained such.

am aware of the similarity which the present process has in common with the processes hitherto proposed first by myself and later by Thomas same purpose, but I consider the present process (even when the same consists of only its first three and main parts) to be novel and distinguished from the said formerly suggested processes not only by its important practical results as the completeness of the lead recovery and the high purity of the resulting lead and blende which could not be attained till now but also by the different ways each single step or part of the present process has to be performed in order to attain these results and as far as the Twynam' process is concerned also by the different character of the series of steps of which each process as a whole is composed of.

I will now proceed to describe every part or step of the process in detail, pointing out their characteristic features on which the mentioned practical results are dependent.

The first or .chloridization step or part of the present process is based lon the well ago discovered reaction which takes place between the chlorids of some metals, particularly zinc chlorid with the sullids of certain other metals as of silver, lead, antimony and arsenic. This reaction can be accomplished in practice in. two ways, either by way of bringing the ore in a fused bath of zinc chlorid, in which case the reaction takes place in a Iiuid medium and the formed chlorids of silver, lead, antimony and arsenic are dissolved in the molten zinc chlorid, or the chloridization can be accomplished by heating the ore with only the equivalent amount of zinc chlorid in which case the reacting mass is in a solid and pulverulent state and the zinc chlorid reacts upon the sulfids particularly in the last stages of the reaction in a gaseous atmosphere and going itself over little by little into vapor due to the fact the vapor tension of the zinc chlorid is very high even at a vtemperature far below its boiling point.

h1s last way of chloridization which serves as the basis and first step of the present process is in many respects the more advantageous one. Apart from requiring much less zinc chlorid (in most cases ten to twenty times less) this way of chloridization takes place under certain conditions much quicker and more complete so that the lead and silver may subsequently be extracted I quantitatively and any antimony or arsenic 1f present 1n the ore may moreover also Twynam for about the under certain conditions be separated and removed in the course of the chloridization operation from the reacting mass, all these features not being attainable when the reaclgior;l takes place in a fused metal chlo'rid I have found however that even by using the gaseous way of chloridization the above mentioned advantageous features as com pleteness and quickness of the reaction, as well as the removal of the antimony and arsenic depend upon the following conditions:

Firstly: upon the correct amount of zinc chlorid added to the ore. If for example the zinc chlorid will be used only as much as required to chloridize the lead sulid as suggested in the Twynam patent the silver sulid and in cases where much antimony and arsenic are present in the ore even the lead sulfid itself may not be decomposed as I found that antimony and arsenic sulids will first be chloridized and that only so much of the lead sulfid will be decomposed as there will be zinc chlorid in excess over that amount necessary for the chloridization of the arsenic and antimony and that the silver sultid will be decomposed only after all the three mentioned -sullids of lead, antimony and arsenic have been decomposed.

Secondly: depend the comp eteness as well as the quickness of the chloridization upon the mixing or agitating of the mass or admixture while the samefis heated; as I have found that the mixture; if heated according to the direction of the Twynam patent in a closed retort or roaster or in any other vessel in which the charge is resting without agitation 'that then only small layers of the mixture near the heating surface will be completely chloridized and that in larger' quantities of the mixture as would be required for working on a commercial scale the inner part of the mass is not completely chloridized and that moreover in such a case the chloridization takes place exceedingly slow. The reason for this phenomenon lays probably in the fact that at a temperature (40G-500 C.) which is much lower than the boiling point of zinc chlorid (7300 C.) the vapor tension 'of latter is not sufiicient to penetrate into the inside of a thick layer of ore unless the gaseous atmosphere or the ore is thoroughly agitated and,

Thirdly: depends the removal of the antimony and arsenic from the chloridized product upon the provision of some device in the chloridizing apparatus so as to admit the volatilizing chlorids of antimony and arsenic to escape from and settle outside of the reacting mass.

In carrying out this chloridizing operation make use of an externally heated furnace such as the drum or tube illustrated in lon-1 gitudinal vertical section in the accompany- V ing drawing. Referring to, this drawing it will be noted that the apparatus comprises a drum or cylinder 1 inclosed within a furnace structure and heated by any suitable means such as the gas burners 2. Within the drum is a rotating shaft 3 carrying stirrer blades 4 which are so arranged as to cause the material in the drum to be progressed from the inlet to the outlet thereof. The shaft and stirrers are suitably driven as by gearing 5 from any convenient source of power and at a speed appropriate for the reaction which takes place within the, drum. The charge is fed into the drum from the hopper 6 by means of the worm 7 driven from the shaft 3. The material enters the drum through theinlet 8 and leaves the drum at outlet 9 at the opposite end which is sealed as shown by being connected to the chamber 10 so as to prevent access of air; a vent 1l is provided leading off volatile fumes, which may be sealed byhaving its outlet dropping below the level of a liquid in a vessel 12; a release valve 13 being provided in the vent pipe 11 a thermometer 14 is provided for indicating the temperature Within the drum.

In such an apparatus, the mixture of ore and of zinc chlorid powder or of the crystals of zinc chlorid double salt is treated to effect the double conversion of the lead and silver sulfid and the sulfids of antimony and arsenic if same are present, into chlorids and the zinc chlorid'into sulfid. There is no necessity of using an excess of zinc chlorid. It was found that even some deficiency in zinc chlorid would not prevent the subsequent quantitative extraction of the lead and silver. The reason for this is that there is always some zinc sulfate in the ore and some is always formed in the course of the chloridization operation which sulfate helpsalong in a direct or indirect way to convert the lead and silver into sulfates which are subsequently extracted by the concentrated metal chlorid solution.

The more suitable temperature for this operation is, in practice, from about 100o to 500o C. or higher.

The apparatus described is particularly advantageous in that it makes the chloridization operation a continuous one land permits heating of the mixture in an economical manner, the material being kept in the form of a stream which moves along the bottom of the apparatus where it is hottest, so that the heating of the charge is rapidly effected. `While the simultaneous mixing and agitating of the charge is essential for the complete as well as for the rapid chloridization of the charge, and for making the operation a continuous one. The agitating prevents at the same time the bottom of the tube fromk burning through while some small amount of air which on account of the agitation may be introduced into or through the tube or .zation. I prefer to do this by means of heating the ore with sulfur or with a sulfur yielding material such as iron pyrites or with any other metal sulfid capable of transferring its sulfur to the metals of the ore. I prefer, however, to combine the suldizing and chloridizing of the ore into one operation by adding to the ore the necessary amount of sulfur or metal sulfid together with the equivalent amount of zinc chlorid and subjecting the admixture to the chloridization operation keeping the temperature preferably below 448 C. the boiling point of sulfur.

The second step of present process consists in leaching out of the pulverulent product resulting from its first step with the object of extracting all the chloridized lead and silver, if latter is also present in the ore.

I have found however that this .object could not be attained by the methods hitherto proposed such as for example in the Twynam patent.

Experiments with lead-zinc ores have shown that even when all their lead and silver were chloridized that these chlorids could not be completely extracted by the mentioned methods, that the extraction of the lead chlorid has shown to be more or less variable but in no case quantitative, while thesilver chlorid was generally not recoverable at all or only to a very small extent.

I have found that this is due to the fact that when the chloridsof lead and silver are brought into solution in the presence of Zinc sulfid a portion of the lead chlorid and practically the whole of the silver chlorid are reconverted back into their insoluble sulfids by the reaction of the zinc sulfid present and are thus not removed by the leaching soli-rf t'lOnS. g 4 K The reversion into sulfids of the lead and silver chlorids has been found by me to be accelerated and considerably increased by the use of warm leaching solutions and is also increased'by prolonging the period of contact between the ore and the leaching solution.

The precautions and'measures to be taken for the purpose of preventing the reaction between the sulfids in the ore and the dissolved lead and silver chlorids may be either mechanical or chemical.

For example the aforesaid reaction may be hindered or minimized b leaching operation under that the temperature aspossible, such as b ing solutions,

leached mass ing out the lixiv thin layers of are against the general pr cases of extracting such ve salts as lead and silver chl cially When the extraction successful) uses the solven sible and for so long a tim The mentioned mechanic ever not very reliable an fore to prevent the afores actions altogether in a c addition lto the leachin substances as Will proh ple Ithe leaching brine) may be acidied from one-half t chloric acid or salt (such as aluminium add to the leaching soluti tion (from 2 to 4% addition Will preve tion of the zinc sulti From the mention however, ,the addi which case the sol or even basic, removal' of bot or of only silv ing solutions chloridizing or such as cupric ferrie sulfate o Such per-chlori leaching soluti and as long as gether the sulfi but also of t above named cannot be used as preventive against the sulfidization of the silv On the other hand it has to be bor that While zinc chlorid serves onl tact substance Witho on the sulfids chl the same,

chlorin and plain chlorid l Further, the aforesai be hindered by treati liminary to the leachi a Way thatsulfid) cont thin film o treating th ing operat ric chlori eXaIIl to a minimum s lation by per lbit the same.

ed substances tion of zinc c on in a ver present in the o orids react on these sulfids liberating hereby f sulfur such as for ex e product previously to ycarrying out the tion of the mass with free sulfur. This such conditions film of sulfur isolates the metal suliids of is maintained as loW the mass and prevents them acting on the y using very cold leachdissolved chlorids. and also by reducing the time Or I may leach first the lead and silver etween the solutions and the or each of them separately without taking uch as by carryany precautions whatsoever and allow the colationthrough whole or a part of same to be turned into Such precautions sulids and leach subsequently the residue actice Which in with a solvent containing a per-chlorid or ry little soluble per-acid. I found that While the lead and orid (and espesilver sulfids in the original ores and metalproves not to be liferous products are very difficult to extract ts as hot as pOS- with solvents containing per-chlorids (or, e as possible. al means are llOW- extracted only when the whole or the d I prefer theremost of the zinc Suld present in the ore is aidundesirable reextracted along with them) the sulfids of hemlcal Way by the lead and silver freshly formed from Ythe g SOlutlOIl 0f SllCll chloridized product are of a particular na- AFOI' ture and are very easily extracted by a per- SolutlOIl (Such aS chlorid Without that much of the blende is by the addition 0f extracted along with them. The reason for el Cent- 0f hydlpthis lies in the fact that the lead and silver liable field ChlOIld being precipitated from their dissolved chlo- ChlOllOl) 0I I may rids by the blende cover the whole of same 011 il Small PIOPOI- with a very fine film of lead or silver sulof zinc chlorid. This ds which then present a large surface to the nt elSOgetlleI the leeeattacking per-chlorid and these freshly d HPOII the lead ClllOI'lOlformed sulfids must, moreover, be first atl PhI'efeI, tacked before the blende can be attacked. lllOlld ln Vhen the lixiviation is done by means of 11111011 Cen be liept neutral a solvent containing a perchlorid such as While OI' the SlmllteneOllS ferrie chlorid it makes therefore practically l1 the leed enel SllVeI' ClllOIldS no difference if the lead and silver are coner chlorid I add t0 the leeelltained in the residue as chlorids or as sulfids Substances WlllCll lla-Ve a formed from such chlorids. In both cases OXdlZlng elleet UPOn SullldS Will they be equally easy extracted as long chlorid, fern@ chlorid, 0I as the ferric chlorid is not used up entirely 1' Per-acids and the like- -in the course of the leaching operation. dS eVen When PIeSent ln the In carrying out the leaching operation Y Small Percentage constituting the second step of the process resent hlnflel' altO- of present invention I use for extracting of dZtlOll not Only 0f the lead only lead chlorid either Water or preferhe Silver ChlOIdS, While the ably a concentrated, solution of a metal Plain chlorids as ZlnC ChlOIlOl chlorid such as the chlorids of calcium mag- SllbStenCeS nesium or sodium (brine solution) and asa el ChlOId. preventive :measure against formation of ne lIl H11-nel lead sulid either mechanical means as for y 21S a 00nexample a very cold solution which is left ut havlng any action for only a short time in contact with the ore Ie the Peror chemical means such as the addition of one ClllOI'diZIlg of the mentioned preventive substances pre1- their active erably, however 2 to 4% of zinc chlorid. going over in protochlorids or The leaching solution may then be used hpt mother Words the mentioned sulids can be or cold but in case I wish to obtain the lead d reactions may also chlorid in crystals the solution must always ng the product prebe used hot.

ng operation in such 'For the extraction of only silver chlorld the metal sulfids (such as zinc I make use of any of its well known solained therein are coated with a vents taking as a preventive measure the ampleby mentioned mechanical means to Which I the leachcount also the treatment of the chloridized ion with a Weak solution of ferproduct preliminary to the leaching operad or cupric chlorid or by agitation for the sake of covering the blende with sulfur or I use as a leaching solution a conc. metal chlorid solution to which an addition of an active chlorid was made such as a per-'chlorid preferably ferrie chlorid.

The extraction of silver chlorid is done at 2. I leach out the first lead chlorid by means of a concentrated metal chlorid solution such as a brine solution containing some lead and 'the silver partly lse zinc chlorid using the same hot or cold but leaving the same so long in contact with the ore till 4all of the silver chlorid is converted into silver sulfid whereupon I leach the residue a second time with a concentrated metal chlorid solution to which a perchlorid such as ferrie chlorid is added to convert the silver sulid into silver chlorid and to simultaneously extract the same.

Instead however of extracting the lead and silver separate each from other I may extract both at the same time in which case I may do it in the following way.

3. I leach with a concentrated metal chlorid solution both chlorids together using as a preventive measure either mechanical means or ferrie case the solution preferably in the cold so as not to cause a'too great loss of its active chlorin, and finally 4. In all cases and' particularly when sil ver is present I may leach first without taking any precautions whatever letting the or wholly to be converted into sulfids and extract the same subsequently'by a cold concentrated meta-l chlorid solution to which ferrie chlorid was added which serves at the same time as a chloridizing as well as a preventing substance.

From the perchlorids in preference to cupric presence of copper interferes sequent recover of the lead.

The active c lorin of the perchlorid is mostly used up in the leaching operation in dissolving some of the zinc sulfd present in the ore and formin anew a certain amount of zinc chlorid which is left in the leaching solution and can be recovered therefrom by evaporation, while its perchlorid or active chlorin contents disappears and has to be renewed at each cycle of the process.

The resulting products of the second art of the process are the residue and the caching solutions. The latter are treated by I use ferrie chloric chlorid because the with the subchlorid, using also in latter the following third and eventually also fourth parts of the process while the residue which represents a blende free from lead, antimony and arsenic is very well adapted for the production of pure lead free zinc products orof a lead free zinc which moreover nhas not to be subjected to the usual zinc refining process. In case however this blende contains much pyrites it is then subjected to a further treatment by the so-called fifth part of present process.

It must be remarked however that while the first two steps of the process are more of a general and preliminary nature having to be applied to all kinds vof ores treated by the present process independent of the particular character of these ores and having also to be applied in the indicated order and succession and before any other step can be undertaken the followingv three steps are more of a speeic nature each serving for the separation or recovery of a certain ingredient as lead, silver or blende andl must not necessarily succeed in the indicated order. They are numbered as third, fourth and fifth rather for the sake of convenience of description.

The third or lead separation part of the process which has for its object the recovery of lead from the extracted lead chlorid in a pure metallic and marketable form I may accomplish in two different ways In the one way I obtain first from the leaching solution the extracted lead chloridin form of its crystals. I do this by making the leaching solution in use hot before the lixiviation. This renders the solution capable of taking up new quantities of lead chlorid and to separate the same as crystals when the solution is cooled to its previous temperature.

The so separated lead chlorid crystals are then dried and fed into a bath of molten zinc chlorid to which a certain amount of metallic lead has been added. Metallic zinc is then added to this bath which dissolves in the molten lead andreduces rapidly the lead chlorid to metallic lead, particularly when the bath is agitated. Successive additions of lead `chlorid and metallic zinc are continuously made. The metallic lead is tapped off after an addition of lead chlorid was made and when the same `1s in excess and the zinc 4chlorid is tapped off after an addition of metallic zinc was made and when the same is being in excess, thereby obtaining two products, metallic lead free from Zinc on the one hand and zinc chlorid free from lead chlorid on the other hand. The so obtained water free and neutral (pure from oxid) zinc chlorid is used in the .first step of the process.

In the other way I reduce the lead chlorid direct from its leaching solution by treating the latter with metallic zinc whereby the lead separates in a spongy state while the equivalent amount of zinc chlorid is formed, and left in the solution.

he spongy lead has hitherto not been found to be readily convertible into commercial form but l have found that if the same is pressed into cakes and then fed into a bath of molten zinc chlorid it can be conveniently remelted and converted into a marketable product. The metallic lead obtained in present process by any of the both indicated ways is of high purity, being particularly free also from any antimony or arsenic and does not require therefore to be subject tothe usual rening process.

The zinc chlorid obtained in solution is recovered therefrom by evaporation and is rey used in the iirst step or in the chloridizacase the zinc chlorid is obtained in a brine solution I recover the same in the form of its double salt with sodium chlorid. l have found that when a brine solution containing zinc chlorid is evaporated it first separates the excess of sodium chlorid contained in solution over and above that amount required for the double chlorid of zinc and sodium while this double salt being a very soluble salt is left in solution and is recovered therefrom by further and separate evaporation thereof to dryness after 'the separated excess of sodium chlorid has been removed. This double salt is very well adapted for the chloridization operation.

Instead however of separating the lead by metallic zinc the latter may be wholly or partly in both the above explained ways of lead separation replaced by the electric current in which case. the zinc chlorid necessary for use in thevlrst step of the process will not be simultaneously recovered with the leadbutchlorin gas will be obtained instead.

tion operationl In This chlorin may however be used for regenerating the active chlorin of the silver chlorid may leachmg solution in which case the so-used up chlorin is `still finally turned into z'inc chlorid whichbeing recovered by evaporation from the le'iachime` solution in the above indicated way is ready to be used in the first ste of the process.

t may also be added that the above described two diiferent ways of lead separation from the lead chlorid leaching solution may both be used at the same time, in such a manner that one part of the extracted lead be separated in crystals while the other part` may be reduced direct from the solution.

The fourth step or silver separation part of the process is used when ores are treated containlng an appreciable amount of silver. We have seen that in such two. Steps of the process have to be adjusted or modified so that along and parallel with the chloridization and lixiviation of the lead a case the first h also the complete chloridization and lixiviation ofthe recoverable silver is brought about. But the fourth 'step has for its object more especially the treatment of the leaching solution containing the extracted silver. ln most of the cases the silver chlorid will be contained in the leaching solution together with more or less of lead chlorid as even when the silver chlorid is leached out separately after the lead chlori d has been leached out the second leaching solution will serve at the same time as a washing to the first leaching solution and will contain therefore some lead chlorid. But the silver can be obtained separately from the lead by precipitating the silver either direct with metallic lead or with any other metal as with zinc oriron which in their turn react on the lead chlorid separating a spongy lead and the latter will separate the silver. @r the silver may also be separated as sulid from the concentrated metal chlorid solution such as a brine solution (in which some zinc chlorid is always present) by means of a metal sulid such as lead sulfid7 zinc sulid, etc., as from such a solution only silver but no other metals will be precipitated as a sulid. A part of the metal or the metal suliid applied for precipitation of the silver will be used up for the reduction of some ferrie chlorid which is always left over after the leaching solution if the same contained ferrie chlorid as a preventive substance, while the main part of the ferrie chlorid or rather of its active chlorin is used up in the leaching operation.

After the precipitated silver 1s separated from the solution the latter contains no activechlorin, the iron salt being all in the form of ferrous chlorid which has now to chloridized by means of chlorin gas to ferrie chlorid so as to return it to its previous strength in active chlorin and make 1t fit for use in the next cycle of the process.

The fifth or iron separation part of present process consists in a magnetic dressing of the residue left over after the second step of the process in orderto extract and separate as much as possible the pyrites from the blende. This lifth step of the process 1s used in the treatment of such lead-zlnc sulfid ores asv are very often found 1n the United. States and Mexico containing much pyrites not easily and expediently separable from the body of the ore. Such ores even 1f freed from their lead contents yield a very inferiorl blende.

The separation of the pyrites from the residue according to present process is based on the novel and surprising observation that the pyrites in the said residue after the same ave gone through the first two steps of the process show to be much more magnetic .than the same were in the original ore, while the blende particles show to have lost at the chlorid corresponding same time much of their original magnetic property.

A magnetic dressing of the said residue has shown therefore to yield two products, a blende and a pyrite-ore, both products of good value not otherwise obtainable in such an easy manner.

Having now fully described my invention and the manner in which the same is to beI performed what I claim is: 1. A process of treatment lead-zinc sulfid ores and metallurgical products consisting of adding to the said ores an equivalent amount of metal chlorid corresponding to the sulfid of lead (as Well as of any arsenicand antimony whichmay also be present in the ore) feeding the said admixture'into a closed and continuously operating furnace heating mixing and progressing the said admixture therethrough and leaching out the formed chlorid of lead from the resultant pulverulent product taking precautions to .revent the reaction between the metal sul- Ads contained in the said product and the said dissolved lead chlorid and recovering the lead in a ure metallic state from the said lead chlorid substantially as described. 2. A process of treatment lead-zinc sulfid ores and metallurgical products containing also silver consisting of adding to the said products an equivalent amount oi' metal chlorid corresponding to the sulfids of silver, lead, antimony and arsenic present, feeding the said admixture into a closed and continuously operating furnace, heating mixing and progressing the said admixture therethrough and leaching out the formed lead.l and silver chlorids from the resultant pulverulent product taking precautions to prevent the sulfidization of Saidlead and silver chlorids andl separating the lead and silver from the leaching solution reco-vering the lead in a pure metallic state substantially as described.

3. A process for recovery of a pure blende` 'from complex lead-zinc sulfid ores contain- `ing also pyrites consisting of adding to the said ore an equivalent amount of zinc to the sulid of lead as well as silver, antimony, and arsenic which may also be present in the ore, feeding the'said admixture into and continuously operating furnace heating, mixing an progressing said admixture therethrough and leaching out the formed lead chlorid from the resultant product taking precautions to prevent the formation of lead suli fid from the lead chlorid and subjecting the resulting blende to a magnetic dressing substantially as described.

4. A process of treatment non-sulid leadzinc ores and metallurgical products consisting of adding to the said ores together with the equivalent, amount of zinc chlorid corresponding to the lead, silver, antimony and arsenic also sulfur' or a metal sulfid capable of sulfidizing the lead and silver present inthe ore, heating and mixing said admixture to form chlorids of lead and silver and leaching out the formed chlorids of lead and silver from the resultant product taking precautions to prevent their sulfidization substantially as described. 'i

5. A process of 'treatment lead-zinc sulfid .ores and metallurgical products consisting ofl adding to the said `ores or products an equivalent amount of metal chlorid such as zinc chlorid required for the chloridization of the lead and silver sulfids feeding -the said` admixture into a closed and continuously operating furnace heating, mixing and progressing the said admixture therethrough allowing the resultant product to cool and leaching the said product with a cold solvent solution (such as brine) to extract the lead and silver chlorids pres-.

ent, the leaching operations being effected in such a Way that the pregnant solution is le ft in contact with thel leached mass for a minimum amount of time, separating the lead and silver from the extracted chlorids recovering the lead in a pure metallic state substantially as described.

6. A process of treatment lead-z/inc sulfid ores and metallurgical products consisting of adding to the said ores an equivalent amount of metal chlorid such as zinc chlorid required for the chloridization of the lead and silver sulfids as Well as of any arsenic and antimony which may also be present in the ore feeding -said admixture into a closed and continuously operating furnace heating mixing and progressing the mixture therethrough leachin out from the resultant pulverulent pro uct first the lead chlorid with Water and then the silver chlorid in the cold With a suitable solvent leaving the same in contact With the leached mass for a minimum amount of time and recovering the lead and silver rom the respective solutions separating the lead in a pure metallic state substantially as described.

7. A process o treatment lead-zinc sulfid ores and metallurgical products consisting of adding to the said material an equivalent amount of metal chlorid such as zinc chlorid required for the chloridization of the lead and silver sulfids as Well as any arsenic and antimony which may also be present in the ore heating such admixture Without access to air treating the resultant mass to cover the particles of metallic sulfids therein with a thin film of sulfur and leaching out the chlorids of lead and silver from the resultant mass with suitable solvents and recovering the lead and silver from theysaid solvents substantially as described.

8. A process for treatment lead and silver sulfid ores and metallurgical products consisting of adding t0 the said ores an equiv- 35 such as zinc chlorid required for the chloridiwith tho necessary amount of Zi alent amount of metal chlorid such as zinc equivalent quantityof zinc chlorid required e5 chlorid required for the `chloridization of for the chloridization of the lead and silver the lead and silver sulids in the ore (as Well sulfids and heating such admixture Without as any arsenic and antimony which may also access to air for the production of a mass be present) heating and agitating such adcontaining lead and silver chlorids removmixture Without access of air leaching out ing the said lead and silver chlorids from 70 the lead and silver chlorids from the resultthe resultant mass by means of lixiviation ant product with a solvent containing subwith a solvent containing ferrie chlorid and .stances Which prevent the reversion of lead thereby preventing the reversion of the said and silver chlorids into sulfids by the rechlorids into sulids substantially as herein- \action of the metal sulfids in the said prodbefore described. 7r uct on the said dissolved chlorids and re 13. A method for the recovery of lead and covering the lead and silver from the leachsilver from sulfid ores and metallurgical ing solutions separating the lead from the products consisting of adding t0 tho Said lead chlorid in a pure metallic state subores `an equivalent amount of metal chlorid stantially as described. such as zinc chlorid required for the chlo- 80 9. A process for the recovery of lead from ridization of the lead and silver sulids in sulfid ores and metallurgical products conthe ore heating and mixing the said admix- SiStiDg 0f adding' t0 the Seid OIeS an eq11 V ture without access to air then removing alent amount Of metal ChlOI'd SllCll aS Z1I1C the lead and silver chlorids by lixiviation chlorid required for the chloridization of with any suitable solvent Without taking any 85 the lead Suld in the Ore heating and I'nlXlIlg precautions for the prevention of the revero SuCh'admXtule WlthOllt eCeSS t0 all* and sion of the said lead and silver chlorids to leaching Out the lead ChlOIld from the I- sulids and finally treating the residue with sultant product with a solvent. sollltlOIl a solvent containing a reagent'which has a benglsuflielently acldlfied 0I COIltlIllIlg s llfchloridizingor oxidizing effect on the sul- 90 fieient ZIIC ChlOIid t0 Prevent the I'SV6I`S-10I1 ids of silver and lead and extracting said 0f lead ClllOlld im@ Sullld and leCOVeIlng lead and silver left back in the residue subthe lead from said lead chlorid 1n apure stantially as descr-moi metallic state substantially as described. 14, In' the treatment of oros 10. A method for the IeCOVeIy 0f lead Eind lurgical products containing lead and silver 95 silver from sulid ores and metallurglcal in a non-su1fid form, the method of omoproducts consisting 0f adding t0 the Sald ridization of said lead and silver consisting ores an equivalent amount of metal chlorld modding to such ores and product and metalzation of the lead and silver sulfids in the also Sulfur 1n a Suitable form 100 `ore heating such admixture without access snlfidizo the load and silver pr t0 all' leaching Out the lead and SllVeI Chloore agitating and heating such admixture rids from the resultant product With'a solvin a Closed furnace snbstontiollv as do- 40 ent `solution containing a reagent which has scribed, l

a chloridizing or oxidizing eliect on sufids 15, In tho treatment of lead Sulfid ores 105 and recovering the lead and SllYeI from the as Set out the method of recgverig from. said leached chlorids substant1ally as dethe load chlorid zino froo lood with Simulscribed. taneous` regeneration of the :zinc chlorid 11. A method for the recovery of lead and used therein consisting of removing the said silver from Suld OI'eS and metelllllglcel lead chlorid formed with a hot solvent solu- 110 products consisting of adding to the said tion cooling` the solution to crystallize out ores an equivalent'amount of metal ChlOIld the dissolvedlead chlorid, melting the said such as zinc chlorid required for the chlocrystals of lead chlorid in a molten bath of ridization 4of the lead and silver suliids in zinc chlorid containing also molten lead the ore heating such admixtures without acinto which metallic zinc is introduced there- 1.15 cess of air, then removing the lead chlorid by reducingthe lead chlorid to metallic lead by lixiviation with a solvent solution conand zinc chlorid tapping olf the recovered taining zinc chlorid under such conditions lead when there is an excess of lead chlorid that the silver chlorid reverts to sulid then and tapping oil' the zinc chlorid when there separately removing the silver by means of a is an excess of metallic zinc substantially as solvent solution containinga reagent which hereinbefore described. has a chloridizing or oxidizing effect on thev 16. In the recovery of lead and silver from silver sulfid (such as cupric chlorid or fersulfid ores containlng the same as set out a.

v60 ric chlorid) substantially as described. method of regenerating the double chlorid 12. A method for the recovery of lead of zinc and sodium from solutions containand silver from sulfid ores and metallurgical ing an excess of sodium chlorid obtained as products containing the same consisting of hereinbefore set out consisting of evaporatmixing the said ores with approximately an ing such a solution until the excess of sodium chlorid is thrown down leaving the double salt of sodium and zine in solution then evaporating to separate out the said double salt which may be reused in the chlordization operation.

17 In the treatment of lead sulfid ores as set vout `the method of transforming the spongy metallic lead obtained in the process in a marketable form by remelting the same from a molten bath containing zinc chlorid 10 substantially as described.

In testimony Whereof'l have signed my name to this specification, in the presence of two subscribing Witnesses.

. SOLOMON GANELIN.

Witnesses:

GEORGE L. BLUME, LEONARD HANERSTEIN. 

